Process for treating oils



u y 1935- 'w. B. D. PENNIMAN 2,007,212 PROCESS FOR TREATING OILS Filed Dec. 15, 1927 s Sheets-Sheet 1 Wmum D. YJQENNMAN.

l N V EN TOR.

ATTORNEY.

y 9, 1935. w. B. D. PENNIMAN PROCESS FOR TREATING OILS Filed Dec. 15 1927 3 Sheets-Sheet 2 mm'em W\LL\AM D. bWENmMAN INVENTOR.

ATTORNEY.

July 9, 1935.

w. B. D. PENNIMAN PROCESS FOR TREATING OILS 'Filed Dec. 15, 19 27 3 Sheets-Sheet 3 mom amm OWN WmmM D. bhmumu INVENTOR.

ATTORNEY.

Patented July 9, 1935 UNITED STATES PATENT OFFICE 2,007,212 PROCESS FOR '1REAT1NG oms William B. D; Penniman, Baltimore, Md.

Application December 15, 1927, Serial No. 240,277 5 Claims. (01. 196-142 This invention relates to the treatment of oils, particularly hydrocarbon oils and more particu-. larly to such processes wherein oils are subjected to the treatment with oxygen containing gases 5 such as air. a In a prior-application of William B. D. Penniman, Serial No. 31,713, filed May 20th, 1925, there are disclosed, methods of oxygenating and disintegrating petroleum or other hydrocarbon oils or similar materials by treatment with air or oxygen under high pressures and temperatures, the hydrocarbon oil desirably being present as a liquid and of depth suilicient to deoxygenate the air during its passage through .such material undergoing treatment. That application discloses various expedients in connection with such treatment such as the inclusion of solid bodies sus-- pended in or carried by the liquid medium and with or without catalysts being present. The temperature specified in that case, may for example be from 300 to 1000 F., but more effective treatment is obtained at temperatures between 600 to 900 F. and particularly from 700 to 850 F. The pressures employed as set' forth in that application may range from slightly above atmosphere to considerably more than atmosphere and as high as 3000 pounds pressure, or in some cases in special apparatus, to even higher pressure. During, the treatment, various products are withdrawn from the treatment chamber or still in the form of vapors and gases, a considerable portion of which is condensable to highly desirable industrial products. Such condensate will generally comprise three main components, namely, 35 water, water-soluble bodies and water insoluble bodies. The presence of such materials will generally lead to segregation to form a two layer condensate, the upper layer of which contains most of the water insoluble material and is generally referred to as motor distillate, while the lower layer will contain most of the water and water soluble bodies. However, since many of the constituents of the two layers are mutually soluble, there will be a partial distribution of the two constituents between the two layers. When desired, the motor distillate may be given several washings with water in limited amounts to avoid undue dilution, these washings, for example, with from 3 to 10% of water for each wash subsequently being added to the water layer. From the water insoluble material, by various treatments, there may be isolated, such materials as acids, p'swils, aldehydes, etc., but a substantial portion of this layer comprises gasoline substitutes of great value. For example, the fraction up to 400 is a gasoline substitute which differs markedly in its properties from the ordinary commercial varieties of gasoline due primarily to its higher content of oxygen containing bodies. It is readily soluble in ordinary 95% alcohol in all proportions and can be mixed 5 with ordinary organic liquids, such'as gasoline, benzol and acetone to form blended fuels for example.

In one run, the water soluble layer was found to contain approximately 18% of organic matenal including acids, mostly acetic, with indications of diabasic acids about 3 aldehydes, principally acetaldehyde and propionaldehyde 7%; ketones including acetone, 3% and approximately 5% of alcohols, both saturated and unsaturated. Such watery fraction may be given a distillation treatment to separate out desirable fractions of material particularly with boiling points between to 90 C. The first few fractions, if the distillation is properly conducted will con- 20 sist-principally of acetaldehyde, while the last fractions will contain a considerable quantity of water. The intermediate fractions containing small amounts of water and having boiling points up to 85. C. are rather complex and were found to contain aldehydes, ketones, alcohols and acids, as well as unsaturated compounds and also compounds formed by combination from the substances mentioned. After separation of the acetaldehyde and desirably after treatment with caustic soda to remove the aldehydes and acids, highly desirable solvents were obtained having a boiling point range for example, from 45- to 85 C. Such a solvent called white solvent" is a clear transparent liquid with a pleasant odor. 5

It mixes in all proportions with water, alcohol,

ether, benzol, and petroleum. It also mixes with gasoline in all proportions and gives to the latter anti-knocking properties. It also mixes with kerosene and reduces its knocking properties in the motor. This white solvent or fractions thereof, is a solvent for shellac, gums, nitrocellulose, and cellulose esters in'general, and when higher alcohols or ethereal salts are present, or combined with organic acids, the solvent properties are substantially improved. Such white solvent or fractions thereof may be used for the extraction of fats and medicinal principles.

' While in the said application, condensation and particularly pressure condensation is one desirable method of treating the efiluent vapors and gases from the oxidation zone, they may also be treated advantageously by other methods either chemical or physical, or both, in order to produce valuable products therefrom. Such treatments ganic acids which may not volatilizepnder the may for example, involve subjection to temperaturcs to obtain thermal treatments, or treatment with absorbents or materials such as fullers earth, bauxite, silica gel etc., or the treatment may be of such a nature as to remove or to modify some or all of the components of the gases and vapors. These treatments may be applied both before and after condensation and either to the entire gaseous and vaporous product or to selected portions thereof.

In addition to the products separated fromthe gases and vapors, the still residues will contain some oxygen containing materials, such as orconditions of treatmenbimposed and also a very high grade'of carbon, together with more or less unoxygenated material, depending on the conditions which have been applied.

Such non-volatile substances may be separated from the residues withdrawn from the still and any unattacked material may be utilized as a portion of the substances utilized in the next treatment. 7

In another application by the same party, Serial No. 42,107, filed July 7th, 1925, a. similar series of treatments are described and carried out under pressures not higher than atmospheric, so that highly desirable products may be obtained in the treatment of such materials as those disclosed in that application under pressures at or substantially below atmospheric. The treatment car- .Iifid out under such lower pressures may not be tlre'pressure is at or below atmospheric. In such multi-stage oxygenation the oil or other material undergoing treatment will pass from the first treatment chamber to a later one, there being as many stills as are found desirable in the treatment of the particular substance utilized under the conditions of temperature and pressure which are imposed. It is not necessary that the conditions prevailingvin each treatment chamber be identical. For example, temperatures in the succeeding chambers may become progressively higher by increments of say F. In addition, the pressure in each still need not be the same. For example, the oil. undergoing treatment may be subjected to superatmospheric pressure at the desired temperature in the initial still. From this still the residual oil may then pass into the next succeeding still where it may be subjected to treatment under pressure less than that in the initial still and so on throughout the battery of stills.

In this way the pressure in the stills may vary from superatmospheric pressure in the initial treatment still or stills to sub-atmospheric pressure in thefinal still or stills. Or if desired, the

treatment of the oil in a series of zones of varying pressures may begin with the use of sub-atmospheric pressure at the desired temperature in the initial still. From this still the residual oil may then be pumped into the next succeeding still where it may be subjected to superatmospheric treatment and so on through the battery of stills. In this modification the pressures in the stills would vary from sub-atmospheric pressure in the initial treatment still or stills to super-atmospheric pressures of several hundred pounds, 200 pounds or higher for example, in the final treatment stills. When using the higher pressures, the stills in which such treatments are carried out should be designed to withstand high pressures as specifically set forth in the copending application No. 31,713 referred to above. The gaseous and vaporous products from the several treatment stills may be combined for treatment but, when using varying pressures in the several stills, it is desirable to treat the effluent products from the several treatment stills separately, particularly when pressure condensation is utilized in connection with the vapors and gases from the high pressure treatment stills.

While in these multi-stage treatments, the residual oil from one still has been stated as pumped or otherwise transferred into a succeeding still, fresh oil of the same character as that originally treated, or 'of other characteristics, maybe added to such residual oils for the subsequent treatment, or any of the by-products of distillation either from still residues or distillates may be rerun either separated or admixed.

In a still further application of the same party, Serial No. 50,108, filed August 13, 1925, there is more specifically set forth asimilar process of treatment carried out as a multi-stage operation, but primarily utilizing super-atmospheric pressures in all of the stills. The number of stills used may vary, depending on the character of the material undergoing treatment and the conditions of treatment which are imposed, but the conditions prevailing in each still or chamber need not be identical, although for best results, the pressures in the stills should be approximately the same and desirably over 300 pounds per square inch, highly advantageous results having been obtained with pressures around 400 pounds. By the use of pumps on the oil lines between the several stills constituting the battery, the oil is readily transferred from one still to the next.

The gases-and vapors from the several treatment stills may be'separately collected and treated or may be combined for treatment. When the conditions for treatment and the materials being treated are substantially the same in each still, the gaseous and vaporous products may be c0nducted to a single condensing train. However, since the overflow from the first still to the next succeeding still, and so on, is usually heavier than the product initially treated, it may prove desirable to treat the gas and vapor products from each oxygenation zone separately. The condensation is desirably carried out-under pressure. In treating the gaseous and vaporous products, fractional condensation is desirable. For this purpose, products coming oiT from the still may be condensed in a condenser using water maintained near its boiling point, for example around 175 F. A portion of the vapors and gases is thus condensed and collected. The remaining gases and vapors are then passed to a second* condenser, desirably kept cold, refrigeration being used when necessary. Scrubbers or absorbers may also be used to remove desired products from the gases.

When using the fractional condensation method, the condensates from the hot water condenser will contain most of the water from the vapor and gas and a-considerable amount of the water soluble organic substances. Some water insoluble material will also be condensed at this point. If sufficient water insoluble material is condensed atthis point, the condensates will stratify into two layers, the upper layer containing most of the water insoluble organic material, and the lower layer containing the water solution of organic substances. The condensate from the cold condenser will also contain some water and water soluble organic products as well as water insoluble organic material. This condensate will also generally stratify upon standing, particularly when removed from the pressure zone. These condensates are treated in substantially the same way as is set forth above for the condensates obtained in the other cases and similar treatments asthose outlined above, may be utilized in the recovery of products from the vapors and gases and also from the residual materials that may be separated from the stills.

In all of the processes outlined above the character of the distillates have been found to be largely determined by a number of factors, the most important of which are indicated below:

First:Character of the hydrocarbon used;

Second:Pressure maintained in the still;

Third:-The temperature maintained in the still;

Fourth:--Sub-division of the air current;

Fifth: Rate of withdrawal of sludge (free carbon content of oil in the still) I Sixthz-Kind and amount of any catalyst used;

Seventh:Presence or absence of neutralizing. agents or other materials that will combine with substances formed during the treatment;

Eighth:The run back of the still head and the temperature maintained therein;

Ninth:The treatment of the vapors while in the still head or by auxiliary apparatus either by chemicals or catalysts for the purpose of altering their composition; and

Tenth:The mode of condensation.

These general factors are important in controlling the character of products produced in the improvements more-specifically set forth be low.

In one utilization of the various products produced under these processes described above, the same applicant in application Serial No. 54,757 filed September 5, 1925, has disclosed the production of motor fuels by the blending of the various substances separated from the eilluent gases and vapors, particularly after treatment to remove therefrom various substances, such as acids, phenols, phenoloid bodies and gum formsome instances by mixing the aforesaid oxygen.

containing products separated from the water soluble materials with the gasoline substitutes derived from the so-called motor distillate particularly having boiling points up to 400 F. or the fraction including material boiling between 400 and 500 F.

The present invention is concerned with the application of the various processes and products described above in connection with the treatment and utilization of other materials than those specified in those applications, and also with the modification and improvement of the processes disclosed in thosecases.

In connection with the more detailed description which is. set forth below by way of illustration and not by way of limitation, the drawings show diagrammatically apparatus which may be used in connection with the processes set forth herein. In such drawings there is shown in Figure 1 a diagrammatic section in elevation of one form of apparafius that may be used in carryingv Fundamentally this invention is concerned which there is no market.

with the oxygenation and disintegration of hydrocarbon oils or other oils and related materials by treatment with air or other oxygen containing gases at increased temperatures and under controlled conditions of pressure. The material being treated is desirably in the liquid or molten state and also is preferably maintained of a depth suflicient to deoxygenate substantially the-air or other oxygen containing gas during its passage through the liquid'or molten material which may contain other materials in suspen- 'sion. The process may be applied to the treatsuch as petroleum oil containing solid substances in suspension, such as powdered coal, coke, peat, and other oxidizable materials. Thus for exam ple, finely divided bituminouscoal may be suspended in petroleum and subjected to the o'xy-- genation treatment. Other substances either solid or liquefiable by heat may be added to the .oil forming the base material of oxygenation.

Ordinarily it is inadvisable to admix substances which are readily disintegrated with those which undergo such transformations with greater difficulty, since the conditions of temperature and pressure usually should be varied to secure most advantageous conversion, specific in each case. However the transformation of one material undergoing treatment with relative case may facilitate the oxygenation of a substance of more difficult oxidizability, and therefore the employment of mixtures of substantially dissimilar oxidizing rates is included, especially when one substance has a stimulating effect on the oxidation of the other.

For example the present process may be utilized for the treatment of rosin oil or pine oil or analogous materials in order to recover valuable products from such materials. The treatment of such materials by the processes herein set forth and more full disclosed in the prior applications referred to above, may yield considerable quantities of organic aliphatic acids such as, for example, propionic and butyric acids and other related acids. Similarly the process may be applied to terpene containing substances in general.

Further the process offers particular advantages in connection withthe treatment of coal tar and particularly such tar derived from low temperature carbonization processes. The developmentof low temperature carbonization on a large scale in this country has been hindered due to the large production of coal tar therein for Ordinary cracking is not sufiiciently effective. By the application of the herein described processes to the treatment of such coal tar, valuable products are derived therefrom among which phthalic acid may be noted as one product that may be produced under chosen conditions of operation.

Asphalt and related materials may similarly be treated desirably by the herein described processes with the production of highly valuable .organic compounds of industrial significance.

As a matter of fact processes outlined in this case produce such organic materials in considerable quantities which may be recovered in ordinary plant equipment in use today so that these processes ofier a ready solution of the question surrounding the utilization of many of the by-products produced in industrial plants.

The reactions taking place in such processes will vary considerably with the particular materials undergoing treatment and in certain instances will produce products not obtainable in the treatment of other materials. For example, in the treatment of terpene containing compounds, there are produced resins of a nature not obtained in substantial quantities and not similar to the resins obtained in the treatment of hydrocarbon materials substantially free from terpene compounds. And during such processes of treatment of the terpene containing materials it is probable that some hydrogen peroxide is formed during the process which due to its peculiar properties, influences the production of various materials in the processes of treating such terpene containing materials.

Not only are the present processes advantageously applied to the materials set forth, but the method of applying those processes is also desirably varied in the production of particular results. For instance, instead of merely'blowing air under pressure through the deoxygenating depth of oil under conditions of temperature and pressure control best adapted to the maximum yield of desired materials, the air under pressure may be blown into a body of oil, fresh oil or residue from a previous operation or a mixture of such materials being added at the point of entry of the air or adjacent thereto so that the 'air and oil mixture is carried along through a treatment zone, i. e. a narrow tube, where it may be preheated, for example, up to about 400 F., or other temperature suflicient to get normal action. Reaction takes place during the passage of the liquid oil and air through the narrow tube, the products of this reaction then passing to a soaking or digesting drum. A substantial level of oil may be maintained in the drum. The heating tube or coil should preferably be placed horizontally, although of course a vertical disposition might be used. Prior to entry of the air and oil into the reaction tube, either or both may be preheated so that upon entry into the narrow tube substantial but normal reaction will be obtained. The temperature in the tube or coil will desirably vary from about 400 F. at the point of entry to approximately 800 F. where the residual oil or air and reaction products enter the soaking or digesting drum. The application of such methods in the present process yields desirable results.

Furthermore, the present processes may be particularly applied in the production of asphalt by air or air blowing of hydrocarbon oils or similar materials. During such process, the asphalt or asphaltic producing bodies should be either liquid as in solution or in emulsion, or molten, so that the air may be passed therethrough. The normal resistance to the passage of air, of such molten or liquid material may be enhanced by the presence of solid bodies or by the use of bailies. When the latter are used they may be so placedas'to produce a specified type of circulation in the liquid undergoing treatment and this may be so arranged that carbon formed in process, will segregate out in a lower portion of the still.

Another factor which influences the separation of carbon and its collection during the process is the position of the nozzle or other device through which the air is admitted to the mate-' rial undergoing treatment. The lower the nozzle is placed in the body of liquid undergoing treatment, the greater is the agitation produced by the entry of the air or other gas so that carbon 6 or other solid material formed during the process is not allowed to settle but is constantly circulated throughout the liquid. By moving the nozzle further from the bottom of the still, however, a quiescent zone may be produced below the air nozzle into which zone the solid particles and carbon may fall and remain until removed from the still.

In making asphalt by these processes, particular attention is paid to the recovery of products from the efiiuent vapors and gases. The treatment of such vapors and gases will followalong the lines more particularly described herein and will result in the production of valuable products other than the asphalt which may be recovered from the still itself. In this way, the application of the herein disclosed processes to the production of asphalt by the blowing of oils leads to decided and substantial improvement in the asphalt industry since very valuable products are obtained from the vapors and gases which ordinarily were lost. In such processes the pressure treatment is particularly applicable either in a single still or in multi-stage operation. The treatment under reduced pressures may also be applied.

The treatment of asphalt base petroleums and particularly those of substantial sulphur content is also desirably carried out with the use of the processes herein set forth. One disadvantage in connection with the treatment of such sulphur containing oils by prior art processes lay in the excessive corrosion to which the apparatus used was subjected.- The applicationof the present processes, however, to the treat 40 ment of such sulphur containing oils or related materials, eliminates substantially corrosion of the apparatus and is, therefore, highly advantageous.

A further advantage which arises from the treatment of sulphur containing materials is the fact that much of this sulphur is converted into acid derivatives such as sulphur dioxide which with the water present formed during the process, forms liquids that serve to hydrate unsaturated material that may be present or formed during the treatment specified. For example, olefines or compounds containing the olefinic linkage are hydrated by water in the presence of sulphuric acid with the formation of alcohol derivatives. This is particularly true in connection with the high temperatures and pressures that are utilized in the pressure treatments which are more desirably used in connection with the treatment of such sulphur containing materials. And still further the sulphur dioxide formed may be separated to a large extent from the efliuent vapors and gases, converted into bisulphite and utilized in the recovery of aldehydes and ketones which are also found in the gases and vapors referred to.

We may also note that due to the complexity of the products produced in the present process, and the temperature and pressure conditions to which they are subjected, there is undoubtedly a reaction or combination between some of the components of the gases and vapors produced herein, with the production of corresponding compounds.

Another feature in connection with the application of the present process lies in the combination of the treatments in the liquid phase with treatments in the vapor phase. For example after subjection of a hydrocarbon oil such as petroleum to a process in accordance with the present disclosure, a vapor phase treatment with oxygenation may be utilized. The vapor phase treatment may be applied either to liquid residue withdrawn from the still or to the vapors and gases formed during the liquid phase treatment, or residue withdrawn from the still may be vaporized and subjected to treatment, such materials being treated separately, simultaneously or in admixture. The vapor phase treatment will generally consist in the subjection of the chosen vapors to the action of oxygen generally in the form of air, although other oxygen containing gases may be used. The temperatures utilized for such treatment will desirably lie in the region of incipient red heat or approximately around 475 to 525 C. Temperatures lower than this will give better results with the materials containing substantial amounts of unsaturated compounds. In the vapor phase treatment catalysts including metals. and metal oxides and their compounds among which are copper, iron, barium oxide and other compounds, or metals, oxides and compounds of the vanadium group of metals and other similar materials may be used. Cooling may be desirably employed in such vapor phase oxidation in order to maintain the temperature in the oxidation zone within prescribed limits since the reaction is highly exothermic. Cooling coils may surround the oxidation zone or cooling agents of the internal type such as steam may be mixed with the gases and vapors undergoing treatment. While the vapor phase treatment is preferably applied to the treatment of the residual vapors and gases from the liquid phase treatment, this order of steps may be reversed so that vapor phase treatment is first obtained, followed by liquid phase treatmentin accordance with one of the herein disclosed processes applied to some or all liquids obtained by condensation from the liquid treating steps.

As set forth above, large quantities of organic products are obtained which include alcohols, aldehydes, ketones, acids, phenols, solvents, gasoline substitutes, gums and other industrial products. Substantial quantities of allyl alcohol have been recovered in some of these-processes. This is a particularly desirable product because of its ready conversion into glycerine by halogenation and saponification; or the allyl alcohol halogenation derivatives may be esterified and the esters utilized as such for solvent purposes, for example, or the halogenation derivatives hydrolyzed to form alcohols and salts.

. Another alcohol'which has been obtained in substantialquantities is methyl alcohol, particularly produced in the treatment of asphalt base petroleum.

Nitrogen compounds derived either by fixation of the nitrogen contained in the air used, or from nitrogen compounds in the stock charged, or'

from both sources, may be recovered. Inorganic derivatives such as nitrates may thus be found for the most part in the water soluble condensates. Organic derivatives such as pyridin is exemplary of water soluble nitrogen compounds that have been found particularly when treating California oils.

The following notes on the treatment of the various compounds or groups of compounds separated from the reaction products are given as exemplary of what may be donewith such products. For example the alcohols may be converted into esters, unsaturated compounds such as olefines, halides, or they may be oxidized either in the liquid or vapor phase to form aldehydes and acids. Such alcohols may be esterified with acids and particularly with the acids produced in the present processes.

The aldehydes obtained may be reduced to form alcohols, or converted into dihalogen substitution products or acetals may be formed from them. Additive compounds, with sodium bisulphite or similar bisulphite, ammonia, hydrocyanic acid and Grignard reagents may also be produced. The acetal preparation may also take place with alcoholic products produced in this process or obtained from outside sources. These aldehyde products may also be subjected to polymerization or to the aldol type of condensation. Condensation with other aldehydes, ketones and acids which may or may not be produced in the present process is also possible. Schiff bases may be produced by reaction with aniline or its homologues. Oximes, hydrazones and substituted hydrazones may also be formed by the usual reactions. The aldehydes may also be subjected to the action of halogens such as chlorine or bromine and their phosphorus derivatives.

Ketones produced herein and separated or not, from the reaction products of the present processes may be reduced to form secondary alcohols or saturated hydrocarbons, or they may be oxidized to form acids. They may be converted into dihalogen compounds, by treatment with phosphorus -pentach1oride, or addition com--'.

pounds with ammonia, sodium bisulphite or similar bisulphite, hydrocyanic acid and Grignard reagents may be obtained. The ketones may besubjected to aldol treatment with other ketones derived from the present process or obtained from extraneous sources. These ketones may further be subjected to condensation reactions similar to those utilized in the conversion of acetone to mesityl oxide, phorone and mesitylene. Ketoximes, phenyl hydrazones and other substituted derivatives, as well as semi-carbazones, may be produced.

The acids obtained from the effluent gases and vapors or from the still residues may be used in the formation of salts, and for the preparation of ketones by distilling the calcium salts, for example; and for the preparation of halides, imides, etc. The acids may be utilized for the formation of anhydrides. These acids may also be subjected to esterification with alcohols 01' unsaturated compounds obtained either from external sources or from the products obtained from the eflluent vapors and gases.

' These various compounds and groups of comounds separated from, the efiiuent gases may also be subjected to the action of an electric current or to electro-chemical treatments to produce valuable compounds therefrom.

In carrying out the processes set forth above the apparatus shown in Figure 1 is particularly desirable for some purposes. That diagrammatic drawing shows by way of example an upright still or. drum having heavy walls adequate to sustain a pressure of 300 pounds per square inch, when pressure treatments are to be utilized. It is preferably formed in two sections A and B, secured together by means of companion flanges 4 and 4 and suitable bolts. The still is mounted ficient pressure merely to overcome the head of the liquid in the still, said air passing through pipe l and coil I 2 (within the still), and depending pipe l3 provided at its lower end which is near the bottom of the still, with an upwardly projected delivery nozzle I4; Blow-cocks l5 enable the level of the oil in the still to be ascertained. A blow-oii' line l6 may be provided through which residual material is removed. l1, I! are thermometer wells. 24 is the vapor line leading to a condenser coil 25 which is connected to a collecting sump 26. The liquid collected in tank 26 is delivered to suitable storage or collecting vessels (not shown), connected to pipe 29. The residual gases pass out through pipe 30. When operating at pressures below atmospheric, instead of the pump 9 and its associated elements, a suction pump 9' may be attached to the pipe 30 through which the residual gases pass, a valve 5| controlling the degree of pressure maintained in the apparatus. The exterior of the still as well as the pipes and other connections for removing vapors and gases may desirably be insulated to prevent deposition of products such as aldehyde resin, or aldehyde or other conden- -sation products, therein.

In Figure 2 there is illustrated diagrammatically apparatus for'carrying out the process where the oil and air react in a tube or coil llll carrying the air inlet I 02 andoil inlet I03. A suitable device l04 for heating the reaction tube at starting of the process, is also shown, but it is generally unnecessary to heat after the reaction has once been started, since by control of the reacting ingredients and other factors described above the temperature in the reaction tube or coil may be maintained within a desirable range; From the reactiontube or coil llll the products pass into the soaking or digesting drum I05 provided with a well I06 from which solid materials or carbon separating in the soaking drum may be recovered. The drum N15 is provided with an outlet pipe I01 through which the efliuent gases and-vapors pass to any desirable treatment apparatus utilized for applying the several treatments thereto specified above.

Figure 3 shows a battery of stills for use in multi-stage oxidation, each still being substantially similar to that in Figure 1. The initial still 225 may be heated at the start of the process by a furnace 226, the stilland furnace being desirably surrounded and reinforced by a concrete and insulating material 221. Stills 226, 229 and 230 may be provided with similar heating apparatus but this is not essential in view of the fact thatthe oil received in this latter still is in a heated condition, being generally derived from the first still 225. The oil after treatment in the still is passed to the next subsequent still by means of pipes 23l, 232 and 233, each of these pipes leading respectively from the upper liquid level of'a preceding still and entering the next succeeding still at a lower point. Air is supplied to the stills preferably at the bottom thereof either by an air compressor 235 or by means of a vacuum pump placed at the residual gas exit as more specifically set forth above, depending on whether pressure treatment or vacuum treatment is applied. The air entering by pipe 236 is provided with suitable branch pipes supplied with the necessary valves for controlling the supply to a distributor 231 in the bottom of the still 225 and similar distributors 238, 239 and 240 in the bottom of each of the other stills. In order that air may be supplied to the distributors at a desired temperature, a coil 242 is shown eontinuing as the pipe 236, which coil may be heated by means of the burner 243, the same having a shut-off valve 244 by which it may either be cut out entirely or regulated as desired, the process not being necessarily dependent upon heating the incoming air. Each of the stills is pro-. vided with a run-back or dephlegmator desirably as a separate chamber not in the still head. Heat interchangers'may also be used if desired. By the use of such run-backs or dephlegmators the type of material whiehis carried out of the still is readily controlled. As it is sometimes found desirable in the way of increasing the efficiency of the treatment process by increasing the percentage of volatile constituents in the product, each still head may be provided with a coil 246 connected to live and superheated steam mains 241 and 248 respectively, controlled by valves 249 and 250, so that the vaporized or oxidized products andgases from the still may be treated at this point at any desired temperature, either by heating or cooling, to assist in the separation of desired'materials. The flow of steam to any or all of the coils 246 may be cut off completely by means of valves 25L In.the dephlegmators a portion of the heavier hydrocarbons, is subtracted from the mixture of gases and hydrocarbons given off by the still, the separation being by condensation and back flow of the heavier materials. From the still heads the hydrocarbons and oxidized materials are carried by and with the gases and vapors, such as nitrogen, steam and any carbon dioxide present through the manifold 210 to the condenser coil 21l which is immersed in cooling liquid in the tank 212. Beneath the cooling tank 212 is a receiving tank 273 for the condensate, the lower end of the coil being arranged to supply into this tank. The tank is closed and provided with a sufiicient gas space above the liquid which space is ventedby a pressure regulated valve 254, the latter being adjust able as to the pressure of release. Other features of the apparatus provided for convenience in handling the material are blow-out pipes 255 leading from the bottom of each tank, the same being controlled by valves 256; and by-pass connections 251, each connected by a three-way valve 258 with the transfer pipes 23!, 232 and 233, the same being valuable to remove the oil undergoing treatment to a common receptacle whenever it is desired, or to transfer the oil from one tank to 'the other opposite to the production of circulation, the universal path for the removal of the oil after treatment being by way of the pipe 259 from the end still 230 of the battery.

The operation of the processes carried out in the apparatus set forth above 'is believed to be sufiiciently set forth by reference to the process treatments previously described, and will not be further stated at this point. But the specific conditions utilized in the treatment of particular oils will be illustrated by the examples set forth below, it being understood that these specific examples are merely exemplary and not limiting, since it is quite obvious that with this disclosure before him, any skilled worker in the art may make various changes and modifications in this disclosure without. departing from the spirit and scope thereof.

One example of the applicationof the present processes is the following applied to an asphalt base oil termed Richmond charging stock, having the following properties:

Richmond fire distillation Temp, Percent Gravity,

F. over A. P. I.

390 Start 494 10 35. 0 527 20 33. 1 559 30 30. 5 591 40 29. 5 600 44 In the treatment of such material the still pressure was approximately 325 pounds per square inch, the still temperature in the oil being from 750 to 780 F. and the still temperature in the head being from 292 to 325 F. 76 cubic feet of air are used to a gallon of oil.

The products recovered may be grouped as follows:

Water distillate, 12.5%.

Water insoluble organic compounds approximately 61%.

Still residues, 24.1%.

In the recoveryof motor fuels or gasoline substitutes from these condensation products, one striking observation may be particularly noted. Whereas ordinary cracked gasoline turns brown on exposure to light, the motor fuels derived from the productsof this invention possess the unique property of bleaching upon exposure to light.

The water distillate was found to contain aldehydes (as acetaldehyde) approximately 2% by volume; ketones (as acetone) 7.0% by volume; and alkyloxy compounds (asmethyl alcohol) 4.9% by volume. terial contained the following:

Alkyl compounds (as methyl alcohol) 0.10% by volume, and also substantial amounts of al dehydes, ketones, and gums or resins. Approximately 26 gallons-of finished gasoline were obtained from the water insoluble material per hundred gallons ofchargin Stock, this gasoline having a gravity of 42.6, and sulphur content of 0.2% and containing approximately 26% of unsaturates. This gasoline was obtained by treat ing the crude water insoluble material with sulphurlc acid of 66 B. and then subjecting to distillation.

The carrying out of the process at varying 'pressures showed that the higher the pressure used, the greater is the yield of methyl alcohol. For this reason for the recovery of methyl alcohol and other oxidation products in higher amounts, high pressure operation may be advantageously'utilized. For example three ILlIlS made at pressures of respectively 275, 325 and 400 pounds yieldedalkyloxy compounds (as methyl alcohol) of the following amounts obtained from the water solution: 4.0%, 4.9% and 6.1%. These The water insoluble ma-- results illustrate the increase in such compounds with the increase in pressure used in the still. Furthermore the gasoline obtained was also found to increase with increasing pressures in the still. In runs corresponding to those mentioned above and utilizing pressures of 275, 325 and 400 pounds respectively, therewas obtained a gasoline yield substantially increasing with the pressure. These figures also show the increase in gasoline product with increase in pressure in the still.

The following notes also indicate the character of products which may be obtained in these processes: A number of fractionations of the water soluble material yielded a series of products. The indication was that there was present about 2 to 3% of esters in the water fraction.

Among the compounds that have been found in the water distillate there may be mentioned saturated and unsaturated alcohols, such as methyl,

ethyl and allyl, aldehydes including acetaldehyde, ketones, particularly acetone, acids such asacetic acid, and derivatives of these compounds, among which are esters such as methyl acetate, ethyl acetate, etc., etc.

The fraction boiling up to 32.5 C. contains about acetaldehyde. The abnormally high boiling point may be due to theformation of constant boiling mixture. The fraction from 525 to 5'7.5 C. appears to contain from 50 to 60% acetone. The distillate from .to C. is liquid, while that from 140 C. to C. is thick and resinous.

A valuable solvent of boiling point 187 C. has been isolated from the water condensate. The high fractions and bottoms from the water layer of the distillate do not appear to be tars but appear to be of a resinous character since they are more or less soluble in water, or readily-soluble in alcohol and ether, and relatively insoluble in hydrocarbon solvents. The residue in the stills appears to be of such a character that it may be mixed with some still bottoms and utilized industrially.

' The tar withdrawn from the still may be used for making insecticidal sprays or spraying compositions, for cattle dips, and the like. Or it may be subjected to treatment for the separation or recovery of various materials therefrom. For'example, it may be subjected to vacuum distillation to yield lubricants suitable for air compressor lubrication, particularly if the oil initially treated is very resistant to cracking. Some fractions may contain siccative oils. Further the tar may be treated to recover particular compounds or groups of compounds therefrom, such as higher alcohols, aldehydes, higher fatty acids (as for soap making), phenols, cresols, resins,- etc. Or the tar may have lime added to it to make a heavy grease similar to Albany grease.

In the operation of the process on California oils, it has been noticed that there is a'tendency for the residuum in the still to form coke or solid asphalt. For example in one run after taking ofl 34.1% of cracked naphtha, in the treatment of charging stock having a specific gravity of 25.2 A. P. I., the residuum had a viscosity of 2040 see. at 130 F., and contained about 14.6% free carbon.

The treatment of oils other than straight paraflin oils appears generally to result in the production of larger quantities of fixed gases such as carbon monoxide, methane, ethane, ethylene, etc., and also appears to run in the direction of formation of larger quantities of ketones such as acetone rather than of aldehydes.

However, control of the operating conditions may be utilized either to increase or decrease the quantities of'fixed gases formed during treatment of any given material, and in general to control either the character or yield of chemical derivatives whether gaseous, liquid or solid.

In order to recover the light products which escape from the condensers with the gases, absorbent media may be used. For example, it was found that by means of activated charcoal it was possible to recover watery distillate, gasoline distillates, etc.

In the treatment of materials by the processes hereinabove set forth, a relatively deep layer or pool of the raw material is used and this layer or pool is generally or desirably made of such depth that under the conditions of treatment, the air or other oxygen containing gas which is passed therethrough is substantially deoxygenated. A layer of at least two or three feet in depth has been desirably employed for this purpose, but as stated, the rate of deoxygenation will vary with the pressure and other conditions imposed.

In carrying out the processes, the material under treatment may conveniently be supplied to the treatment zone in amounts sufiicientto maintain a substantially constant level or depth of such material. I The addition of material for this purpose may be either intermittent or continuous. The constant addition of material into the charge in the oxidizing zone has a tendency to reduce to a minimum the occurrence of ordinary destructive combustion, allowing the formation of valuable products and substantiallyeliminating the hazard of explosive conditions which might prevail should oxygen be present in predominating proportions. In the treatment of hydrocarbon oils by the processes set forth, carbon may be present in the oil either produced by the reactions themselves or added from an extraneous source.

Oxidation of this carbon in the process will supply.

heat while eliminating such carbon which would otherwise remain in the spent sludge or tar drawn from the treatment zone. To the extent that heat is thus supplied by the oxidation of carbon, useful work is performed. If the object isto secure from petroleum or other hydrocarbon oils a substantial proportion of lighter hydrocarbons and a minor degree of oxidation, the heat supplied by the combustion of carbon calls for less oxidation of the hydrocarbons. With this tendency to oxidation of the very fine carbon present which may be in colloidal condition, there is the opportunity of filtering the tar or spent sludge withdrawn from the oxidation zone, thus removing the carbon which may be present, and returning the filtered oil to the treatment zone.

The oxidizing agent desirably'employed is ordinary air, utilized without drying or modification of its normal moisture content, which may vary from time to time. Or it may be dried if desired to a-uniform degree of humidity. Likewise for such purposes, moisture, for example, steam, may be introduced into the treatment zone as for example, with the air. In the processes involving the utilization of high pressures, which in such cases serve to a large measure to prevent premature volatilization of the oil, too drastic a degree of oxidation may be avoided by diluting the air or other oxygen containing gas with steam or other diluent gases, such as the products of com bustion, or with deoxygenated air discharged from the condensers. Steam is however considered to be preferable to exhaust gases, as a diluent in this connection. The enrichment or im overishment of this air will also be determined by the character of the oil or of the products. On the other hand when treating highly resistant organic material such as the spent oils from cracking stills or for securing deep seated oxygenation effects, the air may be enriched with oxygen. Pure oxygen obtained for example, by the liquefaction of air, could be used in this manner. The use of air under high pressure generally supplies heat since the air is preheated by such compression. The temperature of such air may be further increased in some cases by having the air travel through a heat interchanger before entrance into the reaction chamber. The heat interchanger may be arranged to utilize some of the heat of the outgoing gases and vapors. In some cases a coil may be placed in the upper part of the reaction chamber through which the air travels before entering the material under treatment.

The resistance of the material undergoing treatment to the passage of air or other gas therethrough may be enhanced by the presence of carbon or other solid material suspended or formed therein. Fine bubbles of air therefore may travel rather slowly upwardly through the pool or layer of material being treated. As previously noted, the rate of travel may be retarded to an additional degree by the employment of battles or other devices arranged to hinder such upward flow. If the bafiles are arranged in the manner to bring about a circulation of the ofl which tends to cause the carbon and other separated solid material to collect to a considerable degree in the lower part of the reaction chamber, this is advantageous as the tarry material or heavy liquid products remaining from the reaction may be drawn off at the lower part of the chamber, either continuously or intermittently as desired.

Chemical oxidizing agents such as metallic peroxides, hydrogen peroxide, bichromates, permanganates and the like are costly while others less expensive such as bleaching powder, acids of nitrogen, such as nitric acid, etc., may possibly bring about objectionable secondary reactions, e. g., chlorination as well as rapid corrosion of containers or the formation of explosive compounds. The use of air as set forth in the preferred procedure leads, therefore, to many advantages including its ready availability, simplicity of treatment, and relative freedom from objectionable or destructive side reactions. By the employment of compressed air in the pressure processes, the concentration of oxygen in the treatment zone is increased as desired, and enables a degree of chemical change to be brought about in a predetermined or regulable manner, which is surprising and of great chemical significance.

For each substance there exists a critical pressure or more strictly a critical range of pressures yielding a maximum proportion of the most desired products. Below this range inadequate yields or indifierent results appear while above the range as stated, there is danger of destructive effect through condensation, polymerization, etc.

By way of suggestion only, and in no spirit of limitation, it may be suggested that the reactions which ensue in the processes outlined above, when treating hydrocarbons or hydrocarbon materials, initially involve, at least in part, a hydroxylation of the hydrocarbon molecule, that is substituton of hydroxyl for hydrogen. Once such conversion has taken place, subsequent breakdown or conversion of the hydroxylated molecule is relatively simple. While some hydroxylated compounds thus formed are undoubtedly stable under the conditions of operation, treatment of the relatively unstable derivatives results in further oxidation or conversion into derivatives of lower boiling point, or in general, compounds of greater stability under the conditions of treatment.

Aside from the effect of any of the finely divided carbon or sulphur which may be present or added to the oil or other material undergoing treatment, there may be added special activating substances such as aluminum chloride, metal oxides such as those of manganese, lead, iron, chromium, vanadium, zinc, copper, or calcium and the like, to assist in the oxygenation; such substances generally being added in small or catalytic proportions. Larger amounts of alkali substances or bodies having a neutralizing effect, such as quick lime, lime stone, or carbonated alkali may be added in some cases. Alkaline substances such as lime act not only to influence the reactions, but also 'materially reduce corrosion in the still or-treatment chamber. It will be understood, however, that in general for carrying outthe reaction particularly of petroleum oils, no catalytic or activating substance need be used. This is especially true when treating native petroleum or its fractions which have been unchangedby cracking or other treatments. Catalysts, however, sometime may be used more advantageously on rather resistant coal tar distillates, spent oils from cracking stills,

and similar raw materials which have experienced a treatment which tends to render them normally more stable and therefore less readily attacked by oxygen.

The treatment chamber may be of heavy steel plate which if desired, may be of chromium steel or chromium nickel steel or other material fairly resistant to the attack of sulphur, sulphur dioxide and organic acids. The treatment chamber may be made of, or lined with, any desired metal or other material for producing special effects when such are sought. Metals for producing catalytic effects or for minimizing the formation or deposition of carbonmiay thus be utilized. The oxidizing chamber or other treatment vessel is desirably cylindrical with concave or convex heads to withstand high pressures when these are employed. In appearance they may resemble an ordinary direct fired oil still. The cylinder may be placed horizontally or vertically. In the latter position a single distributor placed at or near the bottom will ordinarily serve for the admission and distribution of the air. In the horizontal form, the air may be introduced through a perforated pipe situated along the bot tom and extending from end to end of the oxidation chamber. Movement of air upwardly through the material undergoing'treatment causes the latter to swirl and circulate in a brisk manner, upwardly, then outwardly towards the walls of the vessel, and finally downwardly towards the source of air supply. Such circulation is effective in bringing about good contact between the oil under pressure and the compressed air supplied to it. The air jets can also be so arranged that the movement of oil within the still is such that the heavier products are segregated in a portion of the-still itself or an attachment thereto. The motive power of the air may also be utilized before or after discharge, to move paddles or other mechanical devices as may be desirable for the same purposes. The current of deoxygenated air or'other gas may also be used to propel fresh air or other oxygen containing gas into the reaction zone.

There need be no fire-box or other provision perature of which may be maintained solely by the heat of oxidation generated within the layer or column of oil, or jointly by such heat of oxidation, and the heat supplied by the compression of the air supply when high pressures are used; or by specially fired preheaters for the oil and/or air, when using preheated air or oil or both, so that oil or air may be preheated and introduced into the reaction zone. Desirably the air will be continuously introduced into the reaction chamber while the oil may be introduced either continuously or intermittently. When compressed air is used in the pressure processes, it will be considerably heated by the compression process, and this may be suflicient to preheat the air to the desired degree, but if not, additional heat may be supplied to the air in any desired manner. Such preheating may be applied both to the airor other oxygen containing gas which is introduced into the reaction zone or to such air with any additions thereto such as steam. In the latter event preheated airand steam will be introduced into the reaction chamber.

While as set forth above fire-boxes arenot necessary, the use of such fire-boxes is not precluded, and may be employed when desired. In such event, for example, they may be used only during the initial or starting-upperiod. When the oil has been heatedsufiiciently so that the oxygen of the air will react with it, the air current which may be preheated as set forth above, may be turned on and heat is thenceforth spontaneously generated in the oil. From this point on the fire on the grate when such is used, may be kept at a low point or allowed to subside entirely;

Using a fireless still without fire-box equipment, the oil may be heated in a convenient receptacle to a temperature of say.500 to 600 F. and then charged into the treatment zone. Air,

preferably preheated, is-introduced and with an effective pressure in the chamber the oil begins to oxygenate and the temperature will rise to say 700 or 750 F. at which point it may be retained by adjustment of the air supply, the degree of preheat thereof, and the continuous introduction of preheated raw oil. In short, once an initial charge of oil has been heated to reaction temperature in a chamber continuously supplied with oil, no further application of heat by means of fire box appurtenance is necessary. I

The employment of a continuous feed of raw material undergoing treatment is not without advantage. The level of the oil in the treatment chamber may be kept fairly constant, thus maintaining a column of material of deoxygenating depth; that is of a depth sufficient to permit of the removal from the air supply of substantially all of its oxygen during the course of travel from the point of ingress to the point of exit. It may also be desirable to withdraw a portion of the material continuously from the reaction pool, preferably from the lower part thereof. The rate of withdrawal may be adjusted with respect to the rate of feed of the oil into the chamber to avoid departing materially from a constant level. Instead of continuous feed and discharge, the operation maybe intermittent portion-wise e. g., frequent altering of feeding in portions and withdrawing portions without substantially disturbing the constant level conditions of the reaction pool. Continuous introduction. and

. withdrawal thus suflice to maintain a relatively constant composition in the treatment zone which is sometimes important in securing uniformity of heat development and effective supervision of the apparatus. In view of the fact that the intermittent process yields constantly changing conditions as the treatment progresses and in some cases may finally come substantially to a stand-still, whereby the conditions of operation are constantly changing and there is less effective control, the continuous process is believed to be most desirable in carrying out the process herein disclosed. The continuous feed of oil or other material undergoing treatment also brings about a safer character of operation in that there is always present an abundance of fresh raw material to which the oxygen has access, and therefore the risk of collection of an excess of oxygen at any particular point with consequent violent local reactions, is minimized.

Condensation of the vapors is preferably carried out under conditions, depending to some extent on the conditions prevailing in the reaction chamber. When the pressure process is used the pressure in the condensers will normally approximate that of the treatment chamber. Condensers in such case may be in open communication with the treatment chamber and such pressure drop as may be observed in the different parts of the condensing apparatus will simply be that due to condensation and loss of pressure by friction. However, in the pressure process and particularly in other processes carried out in accordance with this invention a shut-off valve may be provided between the still and condensers to cut off any desired units or to reduce the pressuretherein. Condensation at atmospheric pressure may be utilized. Further the tail gases from the condenser may be treated in various ways such as by absorbent agents, namely; silica gel, absorbent carbon, 'etc., to remove any residual vapors such as light aldehydes and volatile hydrocarbons. The tail gases thus treated will be found to contain a very high proportion of nitrogen which may be purified and used in admixture with hydrogen to make synthetic ammonia. When properly deoxygenated, the tail gases will contain littleor no oxygen, carbon dioxide will be present in but moderate amounts and occasionally there will be present a small proportion of carbon monoxide.-

The condensates obtained in this process are generally acid due to the presence of a variety of organic acids which may include formic, acetic, propionic, butyric and. higher fatty acids of this series, also unsaturated acids such as acrylic, and there may also be present aromatic acids such as phthalic acid or its anhydride. Sulphur dioxide may also be present. For that reason it is desirable to construct condensers or at least that portion in which the acids condense, of material such as copper, chrome steel, nickel chrome steel, monel metal and the like, which are notably resistant to organic acids. Enamel lined condenser tubes may be used if desired.

The material withdrawn from the main treatment still or stills during the treatment and any residue remaining in the still or stills at the end of a particular run, will generally be found to contain valuable products including oxygenated derivatives that are non-volatile under conditions of treatment. For example, fatty acids will be found in such residuum when hydrocarbon oils are being treated. Such valuable products may be recovered if desired, and any residuum returned to the still or stills for retreatment, or such residuum or material withdrawn during the process may be utilized in a subsequent run generally with the addition of fresh raw material.

While the process as set forth above is exemplified by the treatment of hydrocarbon material without any initial treatment, the raw material may first be given a chemical treatment, as, for example, by chlorination, nitration, or sulphonation, or in any other desired way before it is subjected to the processes herein set forth.

In utilizing the vapors and gases which are swept out of the treatment zone by the current of deoxygenating air or any other way, the typical example as given above, makes use of condensation but other treatments either chemical or physical or both, may be applied to these effluent vapors and gases in order to produce valuable products therefrom. For example, they may be subjected to temperature treatments of various kinds; they may be treated with absorbents such as fullers earth, bauxite or silica gel, etc.; or again they may be treated chemically to remove or modify the components or some of them only of the gases and vapors. Such treatments may be applied both before and after condensation, and either to the entire gaseous or .vaporous product or to selected portions thereof. Furthermore the eiiiuent gases and vapors may be subjected to the action of a distilling head which may be carried out in towers under super-atmospheric pressure if desired. In carrying out any of these treatments or fractionations, or for carrying out other fractionations that may prove desirable, bubble towers may be utilized.

In general it should be noted that the process of oxygenation and disintegration herein set forth is essentially different in character from the previous processes known in the art, and particularly those concerned with the treatment of hydrocarbon oils. The products produced in the instant process strikingly emphasize this differentiation.. Furthermore, in the present process, it is possible to obtain yields of more than one hundred percent based on the material undergoing treatment, since there is a combination of oxygen during the treatment.

Having thus set forth my invention, I claim:

1. The process of treating hydrocarbon oils which comprises reacting air and oil together at desired temperatures of from 300-1000 F. and superatmospheric pressures to efi'ect substantially complete deoxygenation of the air, and passing the products from the reaction zone to a soaking or. digesting zone, the air during such treatment being substantially deoxygenated.

2. The process of treating hydrocarbon oils which comprises reacting air and oil together at desired temperatures of from 300-1000 F. and superatmospheric pressures to effect substantially complete ieoxygenation of the air, and passing the products from the reaction zone to a soaking or digesting zone, the air during such treatment being substantially deoxygenated to produce oxygenation and disintegration products, and recovering such oxygenation and disintegration products from the soaking or digesting zone.

3. The process of treating hydrocarbon oils which comprises reacting air and oil together under desired conditions of temperature of from 300-1000 F. and superatmospheric pressure to produce substantially complete deoxygenation of the air during such treatment, and passing the products-from the reaction zone to a soaking or digesting zone. v

4. The process of making hydrocarbon products which comprises passing air through a hydrocarbon oil under conditions of temperature and pressure adapted to deoxygenate said air substantially completely, whereby volatile products and a tar residue including oxygen-containing organic compounds are formed, withdrawing said tar residue and subjecting it to vacuum distillation to recover separable products therefrom.

5. The process of treating hydrocarbon oils which comprises subjecting said oil to treatment with an oxygen-containing gas at elevated temperatures and under controlled pressures, and passing the products from the reaction zone to a soaking or digesting zone, the oxygen-containing gas in contact with said oil being substantially freed of its oxygen content, said oxygen entering into reaction with the constituents of the oil and in part being combined therein to produce oxygen-containing organic compounds, and recovering products from the soaking or digesting zone, said recovered products including compounds containing oxygen bound in the molecule.

WILLIAM B. D. PENNIMAN. 

